US11192873B2ActiveUtilityA1

Process for the preparation of unsaturated carboxylic acids by carbonylation of allyl alcohols and their acylation products

64
Assignee: BASF SEPriority: Feb 24, 2017Filed: Feb 13, 2018Granted: Dec 7, 2021
Est. expiryFeb 24, 2037(~10.6 yrs left)· nominal 20-yr term from priority
Inventors:Mathias SchelwiesRocco PacielloRalf PelzerWolfgang Siegel
C07C 51/09C07C 51/353C07C 51/12C07D 307/92C12P 7/40C07C 67/08C12P 41/005C07C 2601/14C12P 7/62C07B 2200/09
64
PatentIndex Score
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Cited by
29
References
40
Claims

Abstract

The present invention relates to a process for carbonylating allyl alcohols at low temperature, low pressure and/or low catalyst loading. In an alternative embodiment, an acylation product of the allyl alcohol is used for the carbonylation. The present invention likewise relates to the preparation of conversion products of these carbonylation products and specifically of (−)-ambrox.

Claims

exact text as granted — not AI-modified
The invention claimed is: 
     
       1. A process for preparing a composition comprising at least one unsaturated carboxylic acid of the general formula (I) 
       
         
           
           
               
               
           
         
         or a salt thereof, in which 
         R 1  is hydrogen, linear or branched C 1 -C 24 -alkyl, linear or branched C 2 -C 24 -alkenyl having 1, 2, 3 or more than 3 C—C double bonds, unsubstituted C 5 -C 12 -cycloalkyl or C 5 -C 12 -cycloalkyl substituted by 1, 2 or 3 C 1 -C 6 -alkyl radicals or unsubstituted aryl or aryl substituted by 1, 2 or 3 C 1 -C 6 -alkyl radicals, 
         R 2  is hydrogen, linear or branched C 1 -C 24 -alkyl or linear or branched C 2 -C 24 -alkenyl having 1, 2, 3 or more than 3 C—C double bonds, or 
         R 1  and R 2  together with the carbon atom to which they are bonded are unsubstituted C 5 -C 7 -cycloalkyl or are C 5 -C 7 -cycloalkyl bearing 1, 2 or 3 linear or branched C 1 -C 6 -alkyl radicals, 
         in which an allyl alcohol selected from compounds of the general formulae (II.1) and (II.2) 
       
       
         
           
           
               
               
           
         
         is subjected to a carbonylation by reaction with carbon monoxide in the presence of a transition metal catalyst comprising at least one metal of groups 8, 9 and 10 of the Periodic Table of the Elements, wherein the reaction is additionally effected in the presence of at least one organic phosphorus compound as ligand and in the presence of a substoichiometric amount, based on the allyl alcohol, of a compound A) selected from anhydrides of aliphatic C 1 -C 12 -monocarboxylic acids, anhydrides of aliphatic C 4 -C 20 -dicarboxylic acids, anhydrides of cycloaliphatic C 7 -C 20 -dicarboxylic acids, anhydrides of aromatic C 8 -C 20 -dicarboxylic acids and acylated allyl alcohols of the formulae (III.1) and (III.2) 
       
       
         
           
           
               
               
           
         
         in which 
         R 3  is hydrogen, linear or branched C 1 -C 24 -alkyl, linear or branched C 2 -C 24 -alkenyl having 1, 2, 3 or more than 3 C—C double bonds, unsubstituted C 5 -C 12 -cycloalkyl or C 5 -C 12 -cycloalkyl substituted by 1, 2 or 3 C 1 -C 6 -alkyl radicals or unsubstituted aryl or aryl substituted by 1, 2 or 3 C 1 -C 6 -alkyl radicals, 
         R 4  is hydrogen, linear or branched C 1 -C 24 -alkyl or linear or branched C 2 -C 24 -alkenyl having 1, 2, 3 or more than 3 C—C double bonds, or 
         R 3  and R 4  together with the carbon atom to which they are bonded are unsubstituted C 5 -C 7 -cycloalkyl or are C 5 -C 7 -cycloalkyl bearing 1, 2 or 3 linear or branched C 1 -C 6 -alkyl radicals, 
         R 5  is C 1 -C 5 -alkyl, 
         and wherein the reaction is effected at a temperature of not more than 100° C. 
       
     
     
       2. A process for preparing a composition comprising at least one unsaturated carboxylic acid of the general formula (I) 
       
         
           
           
               
               
           
         
         or a salt thereof, in which 
         R 1  is hydrogen, linear or branched C 1 -C 24 -alkyl, linear or branched C 2 -C 24 -alkenyl having 1, 2, 3 or more than 3 C—C double bonds, unsubstituted C 5 -C 12 -cycloalkyl or C 5 -C 12 -cycloalkyl substituted by 1, 2 or 3 C 1 -C 6 -alkyl radicals or unsubstituted aryl or aryl substituted by 1, 2 or 3 C 1 -C 6 -alkyl radicals, 
         R 2  is hydrogen, linear or branched C 1 -C 24 -alkyl or linear or branched C 2 -C 24 -alkenyl having 1, 2, 3 or more than 3 C—C double bonds, or 
         R 1  and R 2  together with the carbon atom to which they are bonded are unsubstituted C 5 -C 7 -cycloalkyl or are C 5 -C 7 -cycloalkyl bearing 1, 2 or 3 linear or branched C 1 -C 6 -alkyl radicals, 
         in which an acylated allyl alcohol selected from compounds of the general formulae (IV.1) and (IV.2) 
       
       
         
           
           
               
               
           
         
         in which R 6  is C 1 -C 5 -alkyl, 
         is subjected to a carbonylation by reaction with carbon monoxide in the presence of a transition metal catalyst comprising at least one metal of groups 8, 9 and 10 of the Periodic Table of the Elements, wherein the reaction is additionally effected in the presence of at least one organic phosphorus compound as ligand and in the presence of water and wherein the reaction is effected at a temperature of not more than 100° C., wherein the carbonylation is not effected in the presence of an added hydrohalic acid and not in the presence of an added alkali metal halide, alkaline earth metal halide or ammonium halide; and 
         wherein the reaction mixture of the carbonylation has a halide content of not more than 2 mol %, based on the total content of allyl alcohol of the general formulae (IV.1) and (IV.2). 
       
     
     
       3. The process according to  claim 1 , wherein the reaction is effected at a pressure of not more than 30 bar. 
     
     
       4. The process according to  claim 1 , wherein the carbonylation is not effected in the presence of an added hydrohalic acid and not in the presence of an added alkali metal halide, alkaline earth metal halide or ammonium halide. 
     
     
       5. The process according to  claim 1 , wherein the reaction mixture of the carbonylation has a halide content of not more than 2 mol % based on the total content of allyl alcohol of the general formulae (II.1) and (II.2). 
     
     
       6. The process according to  claim 1 , wherein the compound A) is selected from acetic anhydride and allyl acetate. 
     
     
       7. The process according to  claim 1 , wherein the compound A) used is an ester of the formula (III.1) or (III.2) that derives from the alcohol of the formula (II.1) or (II.2) used as the reactant for carbonylation. 
     
     
       8. The process according to  claim 1 , in which the reaction is additionally effected in the presence of a nucleophilic reagent selected from 4-(di(C 1 -C 4 -alkyl)amino)pyridine, 4-(C 1 -C 4 -alkyl)pyridine and 4-(1-pyrrolidinyl)pyridine. 
     
     
       9. The process according to  claim 8 , in which the nucleophilic reagent selected from 4-(di(C 1 -C 4 -alkyl)amino)pyridine, 4-(C 1 -C 4 -alkyl)pyridine and 4-(1-pyrrolidinyl)pyridine, is used in an amount of 0.01 to 5 mol %, based on the total molar amount of the compounds (II.1) and (II.2). 
     
     
       10. The process according to  claim 1 , in which the transition metal is used for the reaction in an amount of not more than 0.5 mol %, based on the total molar C amount of the compounds (II.1) and (II.2). 
     
     
       11. The process according to  claim 1 , wherein the transition metal is selected from Pd, Ru, Rh, Ir and Fe. 
     
     
       12. The process according to  claim 1 , wherein the organic phosphorus compound is selected from trialkylphosphines, triarylphosphines, dialkylarylphosphines, alkyldiarylphosphines, cycloalkyldiarylphosphines, dicycloalkylarylphosphines, tricycloalkyl-phosphines, triheterocyclylphosphines and trihetarylphosphines. 
     
     
       13. The process according to  claim 1 , in which the total amount of the compound A) is not more than 50 mol %, based on the total molar amount of the compound (II.1) and (II.2). 
     
     
       14. The process according to  claim 8 , in which the reaction is additionally effected in the presence of a base other than the nucleophilic reagent selected from 4-(dimethylamino)-pyridine, 4-(C 1 -C 4 -alkyl)pyridine and 4-(1-pyrrolidinyl)pyridine. 
     
     
       15. The process according to  claim 1 , in which the reaction is effected in the presence of an added aprotic organic solvent. 
     
     
       16. The process according to  claim 1 , wherein the reaction is effected at a temperature of not more than 80° C. 
     
     
       17. The process according to  claim 1 , wherein the reaction is effected at a pressure of not more than 25 bar. 
     
     
       18. The process according to  claim 1 , wherein the compound of the general formula (II.1) which is used for the reaction is selected from nerolidol, linalool, 3-methyl-1-penten-3-ol, 1-hepten-3-ol and 1-vinylcyclohexanol. 
     
     
       19. The process according to  claim 1 , wherein E-nerolidol is used for the reaction. 
     
     
       20. The process according to  claim 1 , in which E-nerolidol is subjected to a carbonylation, giving a reaction mixture comprising (3E,7E)-4,8,12-trimethyltrideca-3,7,11-trienoic acid or a salt thereof and (3Z,7E)-4,8,12-trimethyl-trideca-3,7,11-trienoic acid or a salt thereof in a weight ratio of 80:20 to 50:50. 
     
     
       21. The process according to  claim 1 , wherein the compound of the general formula (II.2) used for the reaction is farnesol. 
     
     
       22. The process according to  claim 1 , wherein the composition comprising the at least one unsaturated carboxylic acid of the formula (I) is an E/Z isomer mixture of the formula (I) comprising a 3-(E) acid of the formula (I-E) and a 3-(Z) acid of the formula (I-Z) 
       
         
           
           
               
               
           
         
         in which 
         R 1  and R 2  have different definitions and R 1  has a higher priority according to IUPAC; 
         and this E/Z isomer mixture of the formula (I) is subjected to an enrichment of one isomer. 
       
     
     
       23. The process according to  claim 22 , wherein the composition comprising the at least one unsaturated carboxylic acid of the formula (I) is an E/Z isomer mixture of the formula (I) comprising a 3-(E) acid of the formula (I-E) and a 3-(Z) acid of the formula (I-Z), in which, in addition,
 (1) the composition comprising the E/Z isomer mixture of the formula (1), in the presence of an alcohol and of a lipase enzyme, is subjected to an enzyme-catalyzed esterification, wherein the 3-(E) acid of the formula (I-E) is converted at least partly to a 3-(E) ester, so as to obtain a composition comprising the 3-(E) ester, unconverted 3-(E) acid of the formula (I-E) and unconverted 3-(Z) acid of the formula (I-Z); 
 (2) the composition obtained in (1) is separated to obtain a composition depleted of 3-(E) acid of the formula (I-E) and enriched in 3-(Z) acid of the formula (I-Z), and to obtain a composition comprising the 3-(E) ester; 
 (3) the composition obtained in (2) which is depleted of 3-(E) acid of the formula (I-E) and enriched in 3-(Z) acid of the formula (I-Z) is subjected to an isomerization to increase the content of 3-(E) acid of the formula (I-E); and 
 (4) optionally, the 3-(E) ester obtained in (2) is cleaved to obtain the 3-(E) acid of the formula (I-E). 
 
     
     
       24. The process according to  claim 22 , wherein the composition comprising the at least one unsaturated carboxylic acid of the formula (I) is an E/Z isomer mixture of the formula (I) comprising a 3-(E) acid of the formula (I-E) and a 3-(Z) acid of the formula (I-Z), in which, in addition,
 (i) the composition comprising the E/Z isomer mixture of the formula (I) is subjected to an esterification in the presence of an alcohol to obtain the 3-(E) ester and the 3-(Z) ester; 
 (ii) the 3-(E) ester and the 3-(Z) ester obtained in (i) are subjected to a lipase-catalyzed enzymatic hydrolysis, wherein the lipase at least partly cleaves the 3-(E) ester to give the 3-(E) acid of the formula (I-E) to obtain a composition comprising the 3-(E) acid of the compound of the formula (I-E), unconverted 3-(E) ester and unconverted 3-(Z) ester; 
 (iii) the composition obtained in (ii) is separated to obtain a composition comprising the 3-(E) acid of the compound of the formula (I-E) and to obtain a composition comprising unconverted 3-(E) ester and unconverted 3-(Z) ester; 
 (iv) the composition which is obtained in (iii) and comprises unconverted 3-(E) ester and unconverted 3-(Z) ester is subjected to an ester cleavage to obtain a composition depleted of 3-(E) acid of the formula (I-E) or salt thereof and enriched in 3-(Z) acid of the formula (I-Z) or salt thereof; and 
 (v) the composition which is obtained in (iv) and is depleted of 3-(E) acid of the formula (I-E) and enriched in 3-(Z) acid of the formula (I-Z) is subjected to an isomerization to increase the content of 3-(E) acid of the formula (I-E). 
 
     
     
       25. The process according to  claim 23 , wherein the isomerization to increase the content of 3-(E) acid of the formula (I-E) is effected in the presence of an anhydride of an organic acid and a base. 
     
     
       26. A process for preparing (−)-ambrox (VIII) 
       
         
           
           
               
               
           
         
         in which 
         a1) a mixture of (3E,7E)-4,8,12-trimethyltrideca-3,7,11-trienoic acid and (3Z,7E)-4,8,12-trimethyltrideca-3,7,11-trienoic acid obtainable by the process as defined in  claim 1 ; 
         b1) the mixture of (3E,7E)-4,8,12-trimethyltrideca-3,7,11-trienoic acid and (3Z,7E)-4,8,12-trimethyltrideca-3,7,11-trienoic acid is subjected to a separation to obtain (3E,7E)-4,8,12-trimethyltrideca-3,7,11-trienoic acid; 
         c1) the (3E,7E)-4,8,12-trimethyltrideca-3,7,11-trienoic acid is subjected to a reduction to obtain (3E,7E)-homofarnesol (VI); 
         d1) the (3E,7E)-homofarnesol (VI) is subjected to a cyclization to obtain (−)-ambrox (VIII); 
         or 
         a2) a mixture of (3E,7E)-4,8,12-trimethyltrideca-3,7,11-trienoic acid and (3Z,7E)-4,8,12-trimethyltrideca-3,7,11-trienoic acid obtainable by the process as defined in  claim 1 ; 
         b2) the mixture of (3E,7E)-4,8,12-trimethyltrideca-3,7,11-trienoic acid and (3Z,7E)-4,8,12-trimethyltrideca-3,7,11-trienoic acid is subjected to a separation to obtain (3E,7E)-4,8,12-trimethyltrideca-3,7,11-trienoic acid; 
         c2) the (3E,7E)-4,8,12-trimethyltrideca-3,7,11-trienoic acid is subjected to a cyclization to obtain sclareolide (VII); 
         d2) the sclareolide (VII) is subjected to a reduction to obtain (−)-ambrox (VIII). 
       
     
     
       27. The process according to  claim 1 , wherein the reaction mixture of the carbonylation has a halide content of not more than 1 mol %, based on the total content of allyl alcohol of the general formulae (II.1) and (II.2). 
     
     
       28. The process according to  claim 2 , wherein the reaction mixture of the carbonylation has a halide content of not more than 1 mol %, based on the total content of esters of the general formulae (IV.1) and (IV.2). 
     
     
       29. The process according to  claim 2 , wherein the reaction is effected at a pressure of not more than 30 bar. 
     
     
       30. The process according to  claim 2 , in which the transition metal is used for the reaction in an amount of not more than 0.5 mol %, based on the total molar amount of the compounds (IV.1) and (IV.2). 
     
     
       31. The process according to  claim 2 , wherein the transition metal is selected from Pd, Ru, Rh, Jr and Fe. 
     
     
       32. The process according to  claim 2 , wherein the organic phosphorus compound is selected from trialkylphosphines, triarylphosphines, dialkylarylphosphines, alkyldiarylphosphines, cycloalkyldiarylphosphines, dicycloalkylarylphosphines, tricycloalkyl-phosphines, triheterocyclylphosphines and trihetarylphosphines. 
     
     
       33. The process according to  claim 2 , in which the reaction is effected in the presence of an added aprotic organic solvent. 
     
     
       34. The process according to  claim 2 , wherein the reaction is effected at a temperature of not more than 80° C. 
     
     
       35. The process according to  claim 2 , wherein the reaction is effected at a pressure of not more than 25 bar. 
     
     
       36. The process according to  claim 2 , wherein the composition comprising the at least one unsaturated carboxylic acid of the formula (I) is an E/Z isomer mixture of the formula (I) comprising a 3-(E) acid of the formula (I-E) and a 3-(Z) acid of the formula (I-Z) 
       
         
           
           
               
               
           
         
         in which 
         R 1  and R 2  have different definitions and R 1  has a higher priority according to IUPAC; 
         and this E/Z isomer mixture of the formula (I), is subjected to an enrichment of one isomer. 
       
     
     
       37. The processing according to  claim 36 , wherein the composition comprising the at least one unsaturated carboxylic acid of the formula (I) is an E/Z isomer mixture of the formula (I) comprising a 3-(E) acid of the formula (I-E) and a 3-(Z) acid of the formula (I-Z), in which, in addition,
 (1) the composition comprising the E/Z isomer mixture of the formula (1), in the presence of an alcohol and of a lipase enzyme, is subjected to an enzyme-catalyzed esterification, wherein the 3-(E) acid of the formula (I-E) is converted at least partly to a 3-(E) ester, so as to obtain a composition comprising the 3-(E) ester, unconverted 3-(E) acid of the formula (I-E) and unconverted 3-(Z) acid of the formula (I-Z); 
 (2) the composition obtained in (1) is separated to obtain a composition depleted of 3-(E) acid of the formula (I-E) and enriched in 3-(Z) acid of the formula (I-Z), and to obtain a composition comprising the 3-(E) ester; 
 (3) the composition obtained in (2) which is depleted of 3-(E) acid of the formula (I-E) and enriched in 3-(Z) acid of the formula (I-Z) is subjected to an isomerization to increase the content of 3-(E) acid of the formula (I-E); and 
 (4) optionally, the 3-(E) ester obtained in (2) is cleaved to obtain the 3-(E) acid of the formula (I-E). 
 
     
     
       38. The process according to  claim 36 , wherein the composition comprising the at least one unsaturated carboxylic acid of the formula (I) is an E/Z isomer mixture of the formula (I) comprising a 3-(E) acid of the formula (I-E) and a 3-(Z) acid of the formula (I-Z), in which, in addition,
 (i) the composition comprising the E/Z isomer mixture of the formula (I) is subjected to an esterification in the presence of an alcohol to obtain the 3-(E) ester and the 3-(Z) ester; 
 (ii) the 3-(E) ester and the 3-(Z) ester obtained in (i) are subjected to a lipase-catalyzed enzymatic hydrolysis, wherein the lipase at least partly cleaves the 3-(E) ester to give the 3-(E) acid of the formula (I-E) to obtain a composition comprising the 3-(E) acid of the compound of the formula (I-E), unconverted 3-(E) ester and unconverted 3-(Z) ester; 
 (iii) the composition obtained in (ii) is separated to obtain a composition comprising the 3-(E) acid of the compound of the formula (I-E) and to obtain a composition comprising unconverted 3-(E) ester and unconverted 3-(Z) ester; 
 (iv) the composition which is obtained in (iii) and comprises unconverted 3-(E) ester and unconverted 3-(Z) ester is subjected to an ester cleavage to obtain a composition depleted of 3-(E) acid of the formula (I-E) or salt thereof and enriched in 3-(Z) acid of the formula (I-Z) or salt thereof; and 
 (v) the composition which is obtained in (iv) and is depleted of 3-(E) acid of the formula (I-E) and enriched in 3-(Z) acid of the formula (I-Z) is subjected to an isomerization to increase the content of 3-(E) acid of the formula (I-E). 
 
     
     
       39. The process according to  claim 37 , wherein the isomerization to increase the content of 3-(E) acid of the formula (I-E) is effected in the presence of an anhydride of an organic acid and a base. 
     
     
       40. A process for preparing (−)-ambrox (VIII) 
       
         
           
           
               
               
           
         
         in which 
         a1) a mixture of (3E,7E)-4,8,12-trimethyltrideca-3,7,11-trienoic acid and (3Z,7E)-4,8,12-trimethyltrideca-3,7,11-trienoic acid obtainable by the process as defined in  claim 2 ; 
         b1) the mixture of (3E,7E)-4,8,12-trimethyltrideca-3,7,11-trienoic acid and (3Z,7E)-4,8,12-trimethyltrideca-3,7,11-trienoic acid is subjected to a separation to obtain (3E,7E)-4,8,12-trimethyltrideca-3,7,11-trienoic acid; 
         c1) the (3E,7E)-4,8,12-trimethyltrideca-3,7,11-trienoic acid is subjected to a reduction to obtain (3E,7E)-homofarnesol (VI); 
         d1) the (3E,7E)-homofarnesol (VI) is subjected to a cyclization to obtain (−)-ambrox (VIII); 
         or 
         a2) a mixture of (3E,7E)-4,8,12-trimethyltrideca-3,7,11-trienoic acid and (3Z,7E)-4,8,12-trimethyltrideca-3,7,11-trienoic acid obtainable by the process as defined in  claim 2 ; 
         b2) the mixture of (3E,7E)-4,8,12-trimethyltrideca-3,7,11-trienoic acid and (3Z,7E)-4,8,12-trimethyltrideca-3,7,11-trienoic acid is subjected to a separation to obtain (3E,7E)-4,8,12-trimethyltrideca-3,7,11-trienoic acid; 
         c2) the (3E,7E)-4,8,12-trimethyltrideca-3,7,11-trienoic acid is subjected to a cyclization to obtain sclareolide (VII); 
         d2) the sclareolide (VII) is subjected to a reduction to obtain (−)-ambrox (VIII).

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